Textile treating agents and methods of preparing same

ABSTRACT

This invention relates to a process for preparing novel condensation products which comprises the step of reacting formaldehyde with a ketone, having the formula WHERE R is alkyl, and an alkyl carbamate having the formula WHERE R&#39;&#39; is selected from the group consisting of a substituted and unsubstituted alkyl having from 1 to 6 carbon atoms under alkaline conditions, and to novel textile treating agents made by said process.

United States Patent Tesoro Aug. 29, 1972 [54] TEXTILE TREATING AGENTS AND METHODS OF PREPARING SAME [62] Division of Ser. No. 507,649, Nov. 15, 1965,

Pat. No. 3,503,701.

[52] US. Cl. ..260/482 C [51] Int. Cl ..C07c 125/06 [58] Field of Search ..260/482 C [56] References Cited UNITED STATES PATENTS 3,524,876 8/1970 Gregson ..260/482 C Primary Examiner-Lorraine A. Weinberger Assistant ExaminerPaul J. Killos Attorney-Donald J. Howard and J. Bradley Cohn [57] ABSTRACT This invention relates to a process for preparing novel condensation products which comprises the step of reacting formaldehyde with a ketone, having the formula u omen where R is alkyl, and an alkyl carbamate having the formula where R is selected from the group consisting of substituted and unsubstituted alkyl having from 1 to 6 carbon atoms under alkaline conditions, and to novel textile treating agents made by said process.

18 Claims, N0 Drawings TEXTILE TREATING AGENTS AND METHODS OF PREPARING SAME This application is a divisional of application Ser. No. 507,649, filed Nov. 15, 1965, now US. Pat. No. 3,503,701.

This invention relates to the treatment of cellulosic textile materials to produce textiles having improved properties. More particularly, this invention relates to the preparation of novel textile treating agents which impart to cellulosic textiles improved dimensional stability, crease recovery and flat drying (wash/wear) properties. v

It is known to enhance the properties of cellulosic textile materials by treating them with polyfunctional chemical compounds, such compounds generally forming crosslinks between cellulosic chains. Many of these textile treating agents require acidic conditions in order for the reaction with cellulose to occur. Thus, for example, N-methylol derivatives of urea, of cyclic urea derivatives and of alkyl carbamates are effective crosslinking agents for cellulose when used in the presence of acidic or acid forming catalysts. It' is often desirable, however, to prevent acidic substances from contacting either the textile fibers themselves or materials used to treat the fibers, such as dyestuffs, sizes, softeners, and the like. On the other hand, treatment of cellulosic textiles under alkaline conditions is not always satisfacto- Polyfunctional N-methylol derivatives employed to cross link cellulose under acidic conditions, react either incompletely or not at all when used under alkaline conditions. For example, N, N-dimethylol alkyl carbamates cannot be used to modify cellulose in the presence of alkaline catalysts since the resulting products exhibit several undesirable characteristics, including chlorine retention and susceptibility to chlorine damage upon washing with hypochlorite bleaching solutions. Crosslinking agents for cellulose which utilize alkaline conditions, such as the condensates of acetone with formaldehyde disclosed in US. Pat. No. 2,711,971 and in British Patent 955,449, also exhibit a serious failing in that textiles treated with these agents either discolor immediately or upon subsequent washing with alkaline solutions. Accordingly, there is a need for reagents which can react with cellulose under alkaline conditions but which avoid the shortcomings of the alkali catalyzed treatments heretofore known in the art.

It is an object of this invention to provide novel treating agents for the modification of cellulosic textiles.

It is another object of this invention to provide a method for modifying cellulosic textiles under alkaline conditions.

Another object of this invention is to provide modified cellulosic textiles which exhibit enhanced properties of dimensional stability, crease recovery, and flat drying, said properties being durable to laundering under alkaline conditions.

Other objects and advantages of this invention will be apparent from the description that appears hereafter.

In accordance with this invention, novel textile treating agents are prepared by reacting in an alkaline medium formaldehyde with a ketone having the formula CH COR where R is a straight or branched chain alkyl and preferably a lower alkyl having from one to four carbon atoms and with an alkyl carbamate having the formula where R is a substituted or unsubstituted alkyl having from one to six carbon atoms. Suitable examples of R include methyl,ethyl, propyl, isopropyl, butyl, isobutyl and the like, and suitable examples of R include methyl, ethyl, propyl, isopropyl, butyl, hydroxyethyl, hydroxypropyl, alkoxyethyl, alkoxypropyl, and the like. The exact structure of these mixed condensation products is not known, but the condensates serve to impart desirable characteristics to cellulosic textiles under alkaline conditions, as will be shown hereinafter.

The mixed condensation product can be obtained by admixing the formaldehyde, ketone, and carbamate and carrying out the reaction between all of the reactants simultaneously, or the formaldehyde can first be reacted with one of the other reactants (e. g., the carbamate) and the resulting product reacted with the remaining reactant (e.g., the ketone). Alternatively, the formaldehyde can be reacted with mixtures of the ketone and the carbamate. Or, the condensation product can be prepared by mixing a reaction product of ketone and formaldehyde with a reaction product of carbamate and formaldehyde. All of the aforedescribed reactions must be carried out under alkaline conditions. it is quite evident, therefore, that several alternative procedures exist whereby the mixed condensation products of this invention can be obtained.

In general, the mole ratio of the reactants should be at least 2 moles of formaldehyde for each combined mole of the other reactants, i.e., for each mole of (ketone plus carbamate). It is preferred that the mole ratio of formaldehyde:ketonezcarbamate range from 421:1 to 6:1:1, although mole ratios not falling within this range nevertheless produce satisfactory products. It should be noted that the ratio of ketone to carbamate need not be 1:1 but can vary widely provided, of course, that the required ratio with formaldehyde is maintained. The condensation reaction is carried out at a pH ranging from about 8.0 to about 12.0 in either an aqueous of non-aqueous medium. The temperature of the reaction may vary from about 0C to about C, and preferably from about 10C to about 30C, while the reaction time will vary from about 1 hour to about 24 hours, depending upon the extent of reaction desired. It should be noted that, although the structures of the aforedescribed condensation products have not been determined, the products are not merely simple mixtures, but complex equilibria are probably established among various possible derivatives of the ketone and carbamate reactants.

As was mentioned previously, the condensation products of this invention are excellent agents for treating cellulose containing textile materials. In treating cellulosic textiles, a solution of the condensation product is applied to the textile by any conventional means such as by padding, dipping, spraying and the like. The treated textile is then dried and heated, in the presence of an alkaline catalyst, to complete the reaction. A particularly noteworthy feature of the textile treating agents of this invention is that they are stable in the presence of alkaline Catalysts and do not react with a cellulosic substrate until heat is applied. It is thus possible to treat a cellulosic fabric with the new composition, dry the fabric, manufacture a garment from such treated fabric, and subsequently carry out reaction of the agent with the cellulose, thereby setting the garment in a desired configuration. [t is, of course, possible to impregnate a textile material with solutions of the formaldehyde, ketone, and carbamate reagents, and then maintain the impregnated material under wet reaction conditions to permit the reagents to react prior to their reaction with the textile.

in preparing the textile treating solutions, the mixed condensation product can be used in concentrations of from about 3 percent to about 30 percent, by weight, based on the weight of the textile being treated, with the preferred range being from 5 percent to percent. Usually, the amount of agent will vary with the properties intended to be imparted to the textile. Thus, for example, quantities of treating agent ranging from about 3 percent to about 5 percent are generally sufficient to impart dimensional stability, but larger amounts would be required to impart wash and wear properties. The condensation products may be applied from either an aqueous or non-aqueous solution.

The alkaline catalyst employed in treating textile materials is preferably a weak base such as alkali metal acetates, carbonates or bicarbonates, but stronger bases such as alkali metal phosphates can be used. Strong bases such as alkali metal hydroxides and silicates can also be used as catalysts, but the amount of such catalyst must be carefully controlled in order to prevent degradation of the cellulose. When alkali metal carbonates or bicarbonates are employed to catalyze the reaction of the mixed formaldehydeketone-carbamate condensation products, amounts of from about 1 percent to about 10 percent, by weight, are satisfactory with the preferred quantity varying from 2 percent to 6 percent. The catalyst is usually applied to the textile from an aqueous or non-aqueous solvent either in combination with the mixed condensation product or separately. In addition to the catalyst, finishing agents such as whiteners, water repellents, softeners, and the like can be added to the textile treating solution.

As was mentioned previously, the cellulosic textile material treated with the mixed condensation product is heated for a brief time in order to effect the crosslinking reaction. The temperature utilized in this operation may vary from about 80C to about 200C for from about 10 minutes to a few seconds. Exposure of the treated textile for a few seconds at much higher temperatures (approximately 300C) can also be used if an extremely rapid reaction is desired. The heat treatment may be carried out in a forced draft oven, by steam, or by any other convenient method. After the heat treatment, the textile material is washed in order to remove catalyst and other residual soluble material and is then dried by conventional means.

The alkali catalyzed treatment of cellulosic textiles according to the present invention can be combined with a dyeing step wherein reactive dyes are utilized. Since reactive dyes are usually applied to and reacted with cellulose in the presence of alkali, the new reagents are particularly suitable whenever the objective is a simultaneous dyeing and finishing process.

The treating agents of this invention can be employed with textile materials formed either completely from cellulose fiber-containing materials, such as cotton, rayon, linen and the like, or blends thereof with other natural and synthetic fibers, such as wool, nylon, polyesters, acrylics, polyolefins and the like, providing that the cellulosic component comprises at least 30 percent, by weight, of the total fiber weight. The treating agents can be applied at any stage of textile manufacture, namely, fibers, yarns, fabrics or garments. Moreover, the treatment of the invention is applicable to woven and knitted textile materials, as well as to non-woven assemblies.

In the following examples, which further illustrate the embodiments of this invention, all parts given are by weight unless otherwise indicated. The test methods referred to in the examples are as follows:

Crease Recovery: Tensile Strength:

ASTM-D1295-60T (in degrees) Ravel Strip Method-ASTM- Dl682-59T(lbs.) ASTM-Dl424-63 (lbs.)

Stoll Flex Abrader.

lb. head, 2 lbs. toggle; ASTM-Dll-61T (in cycles) Tear Strength: Abrasion Resistance:

Damage Due to: Retained Chlorine: Wash and Wear:

whiteness: Laundering:

EXAMPLE 1 The pH of a mixture of 232 g. (4 moles) of acetone, of 356 g. (4 moles), of ethylcarbamate and of 1,296 g. (16 moles) of 37 percent aqueous formaldehyde solution was adjusted to 10 with 5N sodium hydroxide. The alkaline reaction mixture was heated to 50C. At this temperature, the reaction became exothermic. After each 2-hour period of heating, the pH of the mixture was readjusted to 10 with 5N NaOl-l. After a total heating time of 7 hours the free formaldehyde content of the reaction mixture was 6.3 moles, indicating that 60.5 percent of the formaldehyde present had reacted. The reaction mixture was then neutralized with acetic acid to a pH of 6.8 and stripped in vacuo to a residue weight of 970 g. The crude product obtained was a viscous syrup, which contained only 2 percent water as determined by the Karl Fisher method.

EXAMPLE 2 The pH of a mixture of 174 g. (3 moles) of acetone, of 267 g. (3 moles) of ethylcarbamate, and of 1460 g. (18 moles) of 37 percent aqueous formaldehyde solution was adjusted to 10.0 with 5N sodium hydroxide. The alkaline reaction mixture was heated at 5560C for 12 hours. At intervals of 4 hours, the pH was readjusted to 10 with 5N NaOH. After a total heating time of 12 hours, 40 percent conversion was achieved as determined from the residual free formaldehyde content of the reaction mixture. The reaction mixture was then neutralized to a pH of 6.9 with a few drops of acetic acid and stripped to 848 g. weight in vacuo. The crude product obtained was a viscous syrup which contained only 0.3 percent water as determined by the Karl Fisher method.

EXAMPLE 3 Samples of plain weave cotton fabric (commonly known as 80 X 80 print cloth) were treated with a 15 percent active aqueous solution of the product of EX- AMPLE 1, to which there were added 3.8 percent of potassium bicarbonate. The treatment was carried out on a laboratory padder setting the squeeze rolls at such a pressure as to give 100-106 percent wet pickup. The samples so treated were dried at 60C and then cured under the conditions specified below in a forced draft oven. After curing, the samples were neutralized in dilute acetic acid solution, washed in a non-ionic detergent solution at 60C and dried. The samples were conditioned overnight in a suitable atmosphere (21C, 65% RH) and weighed on an analytical balance to determine the weight increase due to the treatment. The following results were obtained.

Wt. Sample Curing Conditions Gain %N 1 135C, 5 Min. 11.7 0.56 2 163C, 5 Min. 12.9

The physical properties of the treated samples were as follows:

Recovery from Creasing %Damage Caused by Example 3 was repeated, but instead of the product of Example 1, the product of Example 2 was used. The results were as follows:

%Wt. Sample Curing Conditions Gain %N 1 135C, 5 Min. 9.5 0.65 2 163C, 15 Min. 9.2

The physical properties of the treated samples were as follows:

Recovery from Creasing %Damage Caused by Sample Dry Wet Retained Chlorine EXAMPLE 5 Example 3 was repeated, but for comparative purposes the chemicals used were a,a' -dimethylolacetone, (DMA), N, N-dimethylol ethyl carbamate (D- MEC) and mixtures of these two reagents were applied in the presence of potassium bicarbonate in addition to the mixed product prepared as described in Example 1.

l OWF=0n weight of fabric. 1 Caled. from percent N. NOTr-:.-All the above samples were cured at 135 C. for 2 minutes.

The physical properties of the treated samples were as follows:

Recovery Wash/wear Percent from rating '11) 1 shrinkage creasing afterafter 5L whiteness Sample Dry Wet 5L 2 10L W I" Orig. 10L

203 186 1. 5 1. 5 1. 0 2. 0 69 63 262 266 3. 3 3. 5 0. 5 1. 0 39 43 260 256 3. 3 3. 5 O. 5 1. 5 44 63 243 249 2. 8 2. 8 0. 5 1. 5 57 56 245 257 2. 8 2. 0 0. 5 1. 5 56 F 265 266 3. 3 3. 3 0. 5 1. 0 53 59 Untr. control..- 187 164 1.0 1.0 6. 5 5. 5 61 1 TD =Tun1b1e drying. 1 L Launderings.

The strength of the above samples was as follows:

% Damage Caused It is apparent that the sample treated with DMEC only in presence of alkaline catalyst (sample A) exhibits poor crease recovery and excessive chlorine damage; the sample treated with DMA only (sample B) exhibits excessive loss of whiteness, while samples treated with the product of Example 1 or with mixtures of DMEC and DMA give satisfactory performance results.

Any departure from the above description which conforms to the present invention is intended to be included within the scope of the invention as defined by the following claims.

What is claimed is:

l. A process for preparing condensation products which comprises reacting formaldehyde, a ketone having the formula where R is alkyl of one to four carbon atoms, and an alkyl carbamate having the formula where R is an alkyl, hydroxyalkyl or alkoxyalkyl group having from one to six carbon atoms, said reaction being carried out under alkaline conditions.

2. The process of claim 1 wherein the reaction is carried out at temperatures ranging from about C to about 80C.

3. The process of claim 1 wherein the mole ratio of formaldehyde to the other reactants is at least 2 to l.

4. The process of claim 1 wherein said ketone is acetone and said alkyl carbamate is ethyl carbamate.

5. A process for preparing condensation products which comprises, first, reacting formaldehyde with an alkyl carbamate having the formula where Ris an alkyl, hydroxyalkyl or alkoxyalkyl group having from one to six carbon atoms and, second, reacting the resulting product with a ketone having the formula 0 CHaiilR where R is alkyl of one to four carbon atoms, said reactions being carried out under alkaline conditions.

6. The process of claim 5 wherein the mole ratio of formaldehyde to the other reactants is at least 2 to 1.

7. The process of claim 5 wherein said ketone is acetone and said alkyl carbamate is ethyl carbamate.

8. A process for preparing condensation products which comprises, first, reacting formaldehyde with a ketone having the formula Ii OHsCR where R is alkyl of one to four carbon atoms, and, second, reacting the resulting product with an alkyl carbamate having the formula where Ris an alkyl, hydroxyalkyl 0r alkoxyalkyl group having from one to six carbon atoms, said reactions being carried out under alkaline conditions.

9. The process of claim 8 wherein the mole ratio of formaldehyde to the other reactants is at least 2 to l.

10. The process of claim 9 wherein said ketone is acetone and said alkyl carbamate is ethyl carbamate.

11. A process for preparing condensation products which comprises reacting formaldehyde with a mixture of a ketone having the formula 0 GH t ilR where R is alkyl of one to four carbon atoms and an alkyl carbamate having the formula where Ris an alkyl, hydroxyalkyl or alkoxyalkyl group having from one to six carbon atoms, said reaction being carried out under alkaline conditions.

12. The process of claim 1 1 wherein the mole ratio of formaldehyde to the other reactants is at least 2 to 1.

13. The process of claim 1 1 wherein said ketone is acetone and said alkyl carbamate is ethyl carbamate.

14. A process for preparing condensation products which comprises (a) reacting under alkaline conditions formaldehyde with a ketone having the formula ii CHsOR.

where R is alkyl of one to four carbon atoms, (b) reacting under alkaline conditions formaldehyde with an alkyl carbamate having the formula i OHiCR where R is alkyl of one to four carbon atoms, and an alkyl carbamate having the formula where Ris an alkyl, hydroxyalkyl or alkoxyalkyl group having from one to six carbon atoms, said reactions being carried out at a temperature of about 0 to C. under alkaline conditions using at least 2 moles of formaldehyde for each combined mole of ketone plus carbamate.

18. The condensation product of claim 17 wherein said ketone is acetone and said alkyl carbamate is ethyl carbarnate.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIQN Patent No. 3,687, 891 Dated August 29, 1972 Inventor(s) Giuliana C. 'Iesoro It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Example 5, Column 6, line 33, Sample C, under whiteness, 10L, "63' should read 62 Column 6, line 34, Sample E, under Wash/wear rating TD after 10L, "2.0" should read 3.-0 Claim 10, The process of Claim 9" should read The process of Claim 8 Signed and sealed this 6th day of February 1973.

(SEAL) Attsst:

ROBERT GO'I'TSCHALK Commissioner of Patents EDWARD M.FLETCHER,JR. Attesting Officer 

2. The process of claim 1 wherein the reaction is carried out at temperatures ranging from about 0C to about 80C.
 3. The process of claim 1 wherein the mole ratio of formaldehyde to the other reactants is at least 2 to
 1. 4. The process of claim 1 wherein said ketone is acetone and said alkyl carbamate is ethyl carbamate.
 5. A process for preparing condensation products which comprises, first, reacting formaldehyde with an alkyl carbamate having the formula where R'' is an alkyl, hydroxyalkyl or alkoxyalkyl group having from one to six carbon atoms and, second, reacting the resulting product wiTh a ketone having the formula where R is alkyl of one to four carbon atoms, said reactions being carried out under alkaline conditions.
 6. The process of claim 5 wherein the mole ratio of formaldehyde to the other reactants is at least 2 to
 1. 7. The process of claim 5 wherein said ketone is acetone and said alkyl carbamate is ethyl carbamate.
 8. A process for preparing condensation products which comprises, first, reacting formaldehyde with a ketone having the formula where R is alkyl of one to four carbon atoms, and, second, reacting the resulting product with an alkyl carbamate having the formula where R'' is an alkyl, hydroxyalkyl or alkoxyalkyl group having from one to six carbon atoms, said reactions being carried out under alkaline conditions.
 9. The process of claim 8 wherein the mole ratio of formaldehyde to the other reactants is at least 2 to
 1. 10. The process of claim 8 wherein said ketone is acetone and said alkyl carbamate is ethyl carbamate.
 11. A process for preparing condensation products which comprises reacting formaldehyde with a mixture of a ketone having the formula where R is alkyl of one to four carbon atoms and an alkyl carbamate having the formula where R'' is an alkyl, hydroxyalkyl or alkoxyalkyl group having from one to six carbon atoms, said reaction being carried out under alkaline conditions.
 12. The process of claim 11 wherein the mole ratio of formaldehyde to the other reactants is at least 2 to
 1. 13. The process of claim 11 wherein said ketone is acetone and said alkyl carbamate is ethyl carbamate.
 14. A process for preparing condensation products which comprises (a) reacting under alkaline conditions formaldehyde with a ketone having the formula where R is alkyl of one to four carbon atoms, (b) reacting under alkaline conditions formaldehyde with an alkyl carbamate having the formula where R'' is an alkyl, hydroxyalkyl or alkoxyalkyl group having from one to six carbon atoms, and (c) contacting under alkaline conditions the products of (a) and (b).
 15. The process of claim 14 wherein the ratio of the total moles of formaldehyde to the total moles of the other reactants is at least 2 to
 1. 16. The process of claim 14 wherein said ketone is acetone and said alkyl carbamate is ethyl carbamate.
 17. A condensation product obtained by reacting formaldehyde, a ketone having the formula where R is alkyl of one to four carbon atoms, and an alkyl carbamate having the formula where R'' is an alkyl, hydroxyalkyl or alkoxyalkyl group having from one to six carbon atoms, said reactions being carried out at a temperature of about 0 to 80C. under alkaline conditions using at least 2 moles of formaldehyde for each combined mole of ketone plus carbamate.
 18. The condensation product of claim 17 wherein said ketone is acetone and said alkyl carbamate is ethyl carbamate. 